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By shortening solid-state diffusion times, the nanoscale size reduction of dielectric materials-such as ionic crystals-has fueled synthetic efforts toward their use as nanoparticles, NPs, in electrochemical storage and conversion cells. Meanwhile, there is a lack of strategies able to image the dynamics of such conversion, operando and at the single NP level. It is achieved here by optical microscopy for a model dielectric ionic nanocrystal, a silver halide NP. Rather than the classical core-shrinking mechanism often used to rationalize the complete electrochemical conversion and charge storage in NPs, an alternative mechanism is proposed here. Owing to its poor conductivity, the NP conversion proceeds to completion through the formation of multiple inclusions. The superlocalization of NP during such heterogeneous multiple-step conversion suggests the local release of ions, which propels the NP toward reacting sites enabling its full conversion.

The formation of metal nanoparticles (NPs) on surfaces by electrodeposition is of significant interest, particularly with a view to understand the early stages of nucleation and growth. Here, the combination of scanning electrochemical cell microscopy (SECCM) and interference reflection microscopy (IRM) is demonstrated to be a compelling approach for real‐time monitoring of NP dynamics within the SECCM meniscus‐electrode wetted area, through synchronous monitoring in the millisecond range of the electrochemical and optical signatures. Diffraction‐limited entities, undergoing phase changes at the electrode substrate, are readily highlighted and tracked in time, including the onset time for the appearance of NPs and their movement over time. The results strongly implicate the rapid formation, surface diffusion and aggregation of smaller entities (not detectable optically) to produce the larger electrodeposited NPs. By applying SECCM tips of different size, it is also possible to understand how the wetted area (meniscus size) plays a key role in the number of NPs formed, with small tip sizes allowing the formation of single NPs. The SECCM‐IRM approach is expected to be a powerful platform for the study of myriad phase‐formation processes at the nanoscale, particularly by drawing on the possibility of making hundreds or thousands of measurements in fresh surface locations through SECCM technology. [ABSTRACT FROM AUTHOR]

Electrodeposition of earth‐abundant iron group metals such as nickel is difficult to characterize by simple electrochemical analyses since the reduction of their metal salts often competes with inhibiting reactions. This makes the mechanistic interpretation sometimes contradictory, preventing unambiguous predictions about the nature and structure of the electrodeposited material. Herein, the complexity of Ni nanoparticles (NPs) electrodeposition on indium tin oxide (ITO) is unraveled operando and at a single entity NP level by optical microscopy correlated to ex situ SEM imaging. Our correlative approach allows differentiating the dynamics of formation of two different NP populations, metallic Ni and Ni(OH)2 with a <25 nm limit of detection, their formation being ruled by the competition between Ni2+ and water reduction. At the single NP level this results in a self‐terminated growth, an information which is most often hidden in ensemble averaged measurements. [ABSTRACT FROM AUTHOR]

By scrutinizing the trajectory of individual nanoparticles (NPs) in solution, NP tracking analysis (NTA) allows sizing individual NPs and providing meaningful complementary information to single NP electrochemistry. Herein, a model is developed to extend NTA to allow dynamic NP sizing and to analyze the kinetics of growth of NPs in solution. Interpreting the NP trajectories as scaled Brownian motion, Monte Carlo simulations produce stochastic trajectories of growing NPs (under diffusion‐controlled growth). These trajectories are grounds for determining a strategy to estimate the growth parameters of individual NPs from the time evolution analysis of the mean square displacement (MSD) curves. In particular, we evaluate the accuracy and precision of the parameter estimates from MSD analysis. In addition, the strategy is illustrated to depict the homogeneous electrosynthesis of silver NPs from the oxidation of a sacrificial Ag ultramicroelectrode (UME) in Fe2+ solution. Where next? The tracking of nanoparticles (NP) trajectories provides complementary size information to single NP electrochemistry. Monte Carlo simulations are extending such strategy to the case of NPs growing in solution. A strategy is proposed to estimate the growth rate of single NPs from mean square displacement curves. It is illustrated to depict the homogeneous electrosynthesis of silver NPs from the oxidation of a sacrificial Ag ultramicroelectrode. [ABSTRACT FROM AUTHOR]

Abstract: Electrodeposition of nanoparticles (NPs) is a promising route for the preparation of highly electroactive nanostructured electrodes. By taking advantage of progressive electrodeposition, disordered arrays with a wide size distribution of Ag NPs are produced. Combined with surface‐reaction monitoring by using highly sensitive backside absorbing‐layer optical microscopy (BALM), such arrays offer a platform for screening size‐dependent electrochemistry at the single NP level. In particular, this strategy allows rationalizing the electrodeposition dynamics at the single‐NP level (>10 nm), up to the point of quantifying the presence of metal nanoclusters (<2 nm), and probing easier NP oxidation with size decrease, either through electrochemical or galvanic reactions. [ABSTRACT FROM AUTHOR]

Single nanoparticle (NP) electrochemistry detection at a micro liquid|liquid interface (LLI) is exploited using the catalyzed oxygen reduction reaction (ORR). In this way, current spikes reminiscent of nanoimpacts were recorded, which corresponded to electrocatalytic enhancement of the ORR by Pt NPs. The nature of the LLI allows exploration of new phenomena in single NP electrochemistry. The recorded impacts result from a bipolar reaction occurring at the Pt NP straddling the LLI. O2 reduction takes place in the aqueous phase, while ferrocene hydride (Fc-H+; a complex generated upon facilitated interfacial proton transfer by Fc) is oxidized in the organic phase. Ultimately, the role of reactant partitioning, NP bouncing, or the ability of NPs to induce Marangoni effects, is demonstrated. [ABSTRACT FROM AUTHOR]

Electrodeposition, nanopipette, optical microscopy, SECCM, single nanoparticle Keywords: electrodeposition; nanopipette; optical microscopy; SECCM; single nanoparticle EN electrodeposition nanopipette optical microscopy SECCM single nanoparticle 1 1 1 05/04/23 20230502 NES 230502 B The Front Cover b draws a parallel between the hybrid scanning electrochemical cell microscopy-interference reflection microscopy (SECCM-IRM) technique, and its use to monitor the nucleation and growth of silver nanoparticles, and the recording of a performance by a rock band. The stage corresponds to the meniscus-electrode wetted area formed with the SECCM probe. [Extracted from the article]

Latex micrometric beads are manipulated by optical tweezers in the vicinity of an ultramicroelectrode (UME). They are optically trapped in solution and approached the electrode surface. After the electrochemical measurement, they are optically removed from the surface. The residence time of the particle on the electrode is thus controlled by the optical tweezers. The detection is based on diffusional hindrance by the insulating objects which alters the fluxes of the redox Ru(NH3)6 3+ species toward the UME and thus its mass-transfer limited current. We have optically deposited successively 1, 2, and 3 beads of 3-μm radius on the UME surface, and we have recorded the variations of the current depending on their landing locations that were optically controlled. Finally we decreased the current by partially blocking the electroactive surface with a six-bead assembly. The variation of the steady-state current and the approach curves allow for the indirect electrochemical localization of the bead in the vicinity of the UME, not only when the bead is in contact but also when it is levitated at distances lower than the UME radius. These experiments show that single particles or more complex structures may be manipulated in situ in a contactless mode near the UME surface. From comparison with simulations, the electrochemical detection affords an indirect localization of the object in the UME environment. The developed approach offers a potential application for interrogating the electrochemical activity of single cells and nanoparticles. [ABSTRACT FROM AUTHOR]

[Display omitted] • Single nanoparticle coulometry implemented in SECM configuration. • Electrosynthesis of Ag 2 O nanocubes studied in situ by individual sizing and counting. • Ag 2 O nanocubes produced quasi-instantaneously under supersaturation conditions. • Nanocubes growth quantified and their possible aggregation probed in situ. The strategy proposed herein employs the scanning electrochemical microscope in generation/ collection mode to clarify the mechanism involved in the electrosynthesis of metal oxide nanoparticles, NPs. It offers simultaneously both generation of the precursors of the NPs and electroanalysis at a single NP level by nanoimpact coulometry. The former process is operated under controlled fluxes within the wide field of precursor diffusion in the inter-microelectrode gap, thus forming a tunable reaction layer allowing the growth of a size gradient of NPs within this gap. The latter process exploits the much slower diffusion of NPs, spatially frozen, in the near field of a collecting microelectrode. This then makes it possible to dynamically monitor the modes of growth of NPs in situ without perturbing their synthesis. As a proof of concept, the synthesis of Ag 2 O nanocubes, NCs, is described, using an Ag microelectrode to generate Ag+ ions while a facing Au microelectrode both electrogenerates HO− and collects the resulting Ag 2 O NCs. Dynamic analysis of the NCs' reductive electrochemical impacts provides insights into their growth and stability. In particular, it suggests a two-step growth mechanism starting from the quasi-instantaneous nucleation of a > 260 nm nuclei followed by mass-transfer-driven crystallization over the nuclei. [ABSTRACT FROM AUTHOR]

The electrochemical nucleation and growth of nanoparticles (NPs) on an electrode surface at a constant potential is traditionally followed by recording the resulting current density during the experiment. The obtained chronoamperometric transients are average measurements, making it difficult to separate individual NP behaviors and to study their cross-talks. Herein, the recently developed Backside Absorbing Layer Microscopy (BALM) is employed to monitor optically in situ and operando the electrodeposition of silver NPs. This latter technique exploits a pseudo-antireflective and metallic contrast layer and allows both sub-nanometer vertical and sub-micrometer spatial resolutions. The information from the recorded movies is readily exploited to study the NP electrodeposition at the single entity level. The image sequences allow quantifying the local electrodeposition of nanomaterials onto the electrode surface, probing the NP dynamics through the extraction of single optical NP growth transients, and analyzing the effect of the neighboring nuclei on the growth of individual NPs. [ABSTRACT FROM AUTHOR]